Synthesis, Characterization, and Applications of Nucleobase-Functionalized Conjugated Polymers

Understanding the effect of the functional groups at the terminus of the side chains is important for developing conjugated polymers through side chain engineering. Nucleobases, which are known for their multi-functionality, have not been deeply studied as functionality in conjugated polymers due to synthetic challenges. The overarching goal of my dissertation is to design, synthesize, characterize conjugated polymers bearing nucleobase functionality in their side chains and demonstrate their utility in various applications. Stille cross-coupling and direct arylation polymerization are used to synthesize adenine- and thymine-containing conjugated polymers. Monomer design requirements for successful polymerization are studied and conditions that optimize polymerization are identified. Structural, thermal, and photophysical properties of nucleobase-functionalized polymers are studied and compared to non-functionalized homologs to assess the impact of nucleobase functionality. In addition to establishing design-structure-property relationships for these polymers, the ability of nucleobases to chelate metal ions and hydrogen bond were examined. My work highlights that nucleobases in the side chains can help to control thin film properties such as packing, which impacts transport properties, and responsive behaviors and surface assembly. This work shows that the properties of conjugated polymers can be improved and their applicability can be expanded through molecular design that utilizes the functionality and specificity of nucleobases. These outcomes are achieved through careful monomer design and optimization of polymerization conditions.